Binuclear diphosphine-bridged iridium complexes as models for the

Miguel A. Casado, Jesús J. Pérez-Torrente, José A. López, Miguel A. Ciriano, Pablo J. Alonso, Fernando J. Lahoz, and Luis A. Oro. Inorganic Chemis...
9 downloads 0 Views 1MB Size
Download PDF
Organometallics 1985, 4 , 1801-1810

1801

Binuclear Diphosphine-Bridged Iridium Complexes as Models for the Catalytic.Hydrogenationof Alkynes in the Presence of Two Metal Centers. The Structure of [ Ir2C12(CH,02CC=CHC02CH,)2(C0)2(DPM)2],a Product of Alkyne Insertions into Two Ir-H Bonds Bruce R. Sutherland and Martin Cowie" Department of Chemistry, The University of Alberta, Edmonton, Alberta, Canada T6G 2G2 Received November 6, 1984

The reactions of tran~-[IrCl(C0)(DPM)]~ (1) and [Irz(CO)z(~-Cl)(DPM),J[BF4] (2) (DPM = bis(dipheny1phosphino)methane) with Hz and the subsequent reactions of the dihydride products with dimethyl acetylenedicarboxylate (DMA) are reported. Compound 1reacts with HZyielding [Irz~H)zC1z(C0)2~DPM)z1 (3) in which the hydrido ligands are mutually cis on adjacent metals. This product reacts with 1 equiv (6) in which alkyne insertion into only of DMA to give [IrzHC1z(CH30zCC=CHCOzCH3)(CO)z(DPM)~] (4), and one of the Ir-H bonds has occurred. Reaction of 2 with Hz yields [Irz(H)4C1(CO),(DPM)z][BF4] (5), in which the two hydride H2loss from this tetrahydride species yields [Irz(H)z(CO)z(p-C1)(DPM)z][BF,] ligands do not seem to be mutually cis. Compound 5 can also be generated from 3 by chloride ion abstraction using AgBF,. Compound 5 reacts with a twofold excess of DMA in CHzClzto yield [IrzC1z(CH30zCC= (7) as the major product. Alkyne insertion into both Ir-H bonds has occurred, CHC0zCH3)z(CO)z(DPM),1 and the additional chloride ion seems to come from the solvent. Compound 7 crystallizes in the space group PT with a = 15.978 (2) A, b = 20.460 (5) A, c = 21.494 (2) A, CY = 107.86 (2)O, 0 = 90.46 (2)O, y = 106.17 ( 2 ) O , and 2 = 4. The structure, which confirms that alkyne insertion into each of the Ir-H bonds of the precursor has occurred, has refined to R = 0.061 and R, = 0.090 based on 11275 observations and 545 parameters varied.

Introduction Much of the present understanding of the mechanisms of homogeneous hydrogenation of unsaturated organic substrates comes from studies on mononuclear rhodiumphosphine comp1exes.l More recent studies have centered on the use of complexes containing more than one metal center as catalysts because of the potentially new modes of reactivity not available with mononuclear system^.^^^ The functions of the different metal centers in these polynuclear complexes is especially intriguing. Reports of alkyne hydrogenation under mild conditions by the binuclear complexes [Rhz(CO)z(p-C1)(DPM)z] [BPh4],4 [Rhz(CO),(DPM),],5 and [RhzCl,(p-CO)(DPM),]6 caused us to question how the two metal centers in these complexes were involved in the catalysis; although it was attractive to consider that both metals were participating, perhaps in a cooperative manner, it was not clear from the studies reported that this was the case. We have recently been studying binuclear, DPM-bridged complexes of iridium as models for multicenter metal catalysts7+ and decided to expand these studies to include alkyne hydrogenation. It was felt that with iridium we might be able to isolate complexes which would model intermediates in the rhodium-catalyzed reactions and by (1) James, B. R. "Homogeneous Hydrogenation"; Wiley: New York, 1974. (2) Fryzuk, M. D.; Jones, T.; Einstein, F. W. B. Organometallics 1984, 3, 185. (3) Burch, R. R.; Shusterman, A. J.; Muetterties, E. L.; Teller, R. G.; Williams, J. M. J. A m . Chem. SOC.1983, 105, 3546. (4) Sanger, A. R. Prepr.-Can. S y m p . Catal. 1979, 6th, 37. (5)Kubiak, C. P.; Woodcock, C.; Eisenberg, R. Znorg. Chem. 1982,21, 2119. (6)Cowie, M.; Southern, T. G . Inorg. Chem. 1982, 21, 246. (7) Cowie, M.; Sutherland, B. R. Znorg. Chem. 1984, 23, 2324. (8) Cowie, M.; Sutherland, B. R., Organometallics 1985, 4 , 1637. (9) Cowie, M.; Sutherland, B. R., submitted for publication.

0276-7333/85/2304-1801$01.50/0

so doing we might gain an insight into these reactions and in particular gain some understanding of how the two adjacent metal centers functioned in catalysis; with the rhodium complexes no intermediates had apparently been observed.,+ Herein we report the initial results of this study.

Experimental Section All solvents were appropriately dried and distilled prior to use and were stored under dinitrogen. Reactions were performed under standard Schlenk conditions using dinitrogen which had been previously passed through columns containing Ridox and 4A molecular sieves to remove traces of oxygen and water, respectively. Hydrated iridium(II1) chloride was obtained from Johnson-Matthey and bis(dipheny1phosphino)methane (DPM) was purchased from Strem Chemicals. Carbon monoxide was obtained from Matheson and used as received. trans-[IrCl[BFd (2) were (CO)(DPM)IZ(1) and [I~z(CO)Z(~-C~)(DPM)~I prepared by the previously reported procedure^.^ Variable-temperature 31P(1HJ NMR spectra were run on a Bruker HFX-90 spectrometer with Fourier transform capability operating at 36.43 MHz. The spectra were measured with an external acetone-d6 lock, and chemical shifts were referenced to 85% H3P0,. *HNMR spectra were run on a Bruker WH-400 spectrometer unless otherwise stated. Infrared spectra were run on a Nicolet 7199 Fourier transform interferometer either as solids in Nujol mulls on KBr plates or as solutions in NaCl cells with 0.5-mm window path lengths. Analyses were performed by the microanalytical service within the department. Preparation of Compounds. (a) [Ir2(H)zC12(CO)2(DPM)2] (3). An atmosphere of hydrogen was placed over a solution of tr~ns-[1rCl(CO)(DPM)]~ (1) (200 mg, 0.156 mmol) in 10 mL of

CHzClz,and the mixture was stirred for 15 min, during which time the color changed from dark purple to light yellow. The solution was concentrated to a volume of 5 mL under hydrogen, and 30 mL of hexanes was added resulting in the precipitation of a pale yellow powder. The solid was collected and dried under a stream of hydrogen. Recrystallization from toluene/ hexanes yielded 3, with 1 equiv of toluene of crystallization, as a colorless microcrystalline solid in 90% yield. Compound 3 was determined to 0 1985 American Chemical Society

Sutherland and Couie

1802 Organometallics, Vol. 4 , N o . 10, 1985 Table I. Spectral Data for the Compoundsn infrared cm-' compound solidb solution' [Ir,(H),Cl,(CO),(DPM),] (3) 2012 (vs), 1972 (st),' 2009 (st, br), 1971 (m, br),e 2091 (m), 2222 (w)' 2073 (w, br), 2098 (sh, br), 2232 (w)' [Irz(H),Cl(CO),(DPM)zl[BF,] (4)

2038 (st), 2073 (vs),' 1964 (w),-9.6 (m) 2147 (m), 2221 ( w ) f

[Ir2(H)2(CO),(p-Cl)(DPM)z]-1934 (vs),' 2067 (st)' [BF,I ( 5 ) [Ir2(H)(CH30,CC= 1982 (vs),' 2131 ( w ) , ~ 1987 (vs), 2004 ( v s ) , ~2148 CHCOzCH,)Cl,(C0)21712 (st): 1623 (w)* (w)' (DPM)zI (6) [Ir,(CH30,CC= CHCOZCH,),Cl2(CO)2(DPM)21 (7)

NMR 31P(1HJ -1.4, -8.6 (m), -5.2 (s),',~-7.6 (m)'

1987 (vs), 1947 (m),e 2002 (st), 1963 (m)? 1706 (vs)? 1582 (mIh

-1.3 (s) -2.8, -16.5 (m)

-12.5, -16.5 (m)

'H 6 7.6-7.1 (m, 40 H), 5.0 (br, 4 H), -5.76 (t, 'Jp.H = 14.4 Hz), -15.10 (t, 'c7p-H = 14.4 Hz),' -14.86 (t, ,Jp.H = 12.5 HZ)~ 7.7-7.2 (m, 40 H), 5.04 (m, 2 H), 4.97 (m, 2 H), -10.00 (br, 1 H), -14.02 (br, 1 H), -14.46 (br, 1 H), -16.59 (t, 1 H, 2Jp_H = 11.1 Hz) 7.55-7.34 (m, 40 H),4.17 (s, 4 H), -13.50 (br t, 2 H) 7.05-7.81 (m, 40 H), 5.19 (m, 2 H), 4.47 (m, 2 H), 3.85 (s, 1 H), 3.21 (s, 3 H), 2.97 (s, 3 H), -8.89 (t, 1 H) 7.43-6.92 (m, 40 H), 5.74 (m, 2 H), 4.81 (m, 2 H), 4.49 (s, 1 H), 4.75 (s, 1 H), 3.19 (s, 3 H), 3.28 (s, 3 H), 3.46 (s, 3 H), 3.48 (s, 3 H)

abbreviations used: st = strong, vs = very strong, med = medium, w = weak, sh = shoulder, s = singlet, m = multiplet, br = broad, t = triplet. *Nujol mull. cCH,Cl, solution. d V s . 85% H,PO,. eu(CO). fu(1r-H). gu(C=O) of C02CH3. hu(C=C). '-40 'C. '-100 "C. kDue to an additional product; see text.

be nonconducting in CH2Cl, solutions ( ~ i ( l O M) - ~ 5 0.5 Q-' cm2 acetylenedicarboxylate (DMA) (15.2 pL, 0.156 mmol) which mol-') but in nitromethane A(10T3M) = 61.1 Q-' cm2 mol-'.'O produced an immediate color change from pale yellow to bright yellow. The solution was allowed to stir for 12 h, during which Spectroscopic parameters for this and all subsequent compounds time a yellow solid precipitated from solution. Diethyl ether (30 are given in Table I. Anal. Calcd for Ir,Cl2P4OzCSgH,: C, 51.57; H, 3.96. Found: C, 51.64; H, 4.05. d) was added to ensure complete precipitation, and the resulting solid was collected and washed with two 10-mL portions of diethyl (b) [Irz(H)4C1(CO),(DPM),I[BF4] (4). An atmosphere of ether and finally dried under an N,stream giving 6 as a yellow hydrogen was placed over a solution of [Ir2(C0),(p-C1)(DPM),J[BF,] (2) (200 mg, 0.150 mmol) in 5 mL of CH2C12,and microcrystalline solid in 90% yield. Compound 6 was determined the mixture was stirred for 15 min resulting in a color change from to be nonconducting in CHzCl2solutions (A(W3M) 5 0.5 Q-' cm2 dark red to light yellow. The solution was taken to dryness under mol-'). Anal. Calcd for Ir2C14P406C59H54: C, 46.96; H , 3.61. Found: C, 46.97; H, 3.69. a rapid flow of hydrogen leaving a pale yellow powder which (e) [Ir,Cl,(CH302CC==CHCOzCH3)2(CO)2(DPM)2] (7). T o proved to be susceptible to decomposition except when kept sealed a solution of 5 (200 mg, 0.150 mmol) in 10 mL of CH2C12under under an atmosphere of hydrogen. For this reason no elemental dinitrogen was added an excess of DMA (50.0 pL, 0.513 mmol) analyses could be obtained. which produced an immediate color change from yellow to orange. (c) [Ir2(H)z(CO),(p-C1)(DPM),I[BF,I (5). Method A. An The solution was allowed to stir for 12 h, after which time 30 mL atmosphere of hydrogen was placed over a slurry of [Ir,(CO)2of diethyl ether was added resulting in the precipitation of a bright (p-Cl)(DPM),][BF,] (2) (200 mg, 0.150 mmol) in 10 mL of THF yellow flocculent solid. The solid was dissolved in acetone and and the mixture stirred for 15 min, during which time all of the placed on a chromatography column containing 100 mesh Florisil. solid disappeared leaving a clear light yellow solution of 4. The Elution with acetone gave one bright yellow band which was hydrogen atmosphere was replaced by one of dinitrogen, and the collected as a yellow solution. The solution was taken to dryness solution was refluxed for 20 min. During this time the color under vacuum giving a bright yellow solid. Recrystallization from changed to a very intense yellow and a bright yellow flocculent CH,Cl,/diethyl ether gave 7 as bright yellow crystals in 50% yield. precipitate appeared. The mixture was taken to dryness under Compound 7 was determined to be a nonelectrolyte in both CH,Cl, an Nzstream giving 5 as a bright yellow powder. Recrystallization and nitromethane solutions. Anal. Calcd for Ir2C12P4010C64H58: from CH,Cl,/diethyl ether gave 5 as a bright yellow microcrysC, 49.07; H, 3.73. Found: C, 48.78; H , 3.91. talline solid in 90% yield. A CH,Cl, solution of this solid proved X-ray Data Collection. Crystals of [Ir2C12(CH302CC= to be a 1:1 electrolyte (A(10-3 M) = 54.2 Q-' cm2 mol-'). Anal. CHC0,CH3)2(CO)z(DPM)2](7) of suitable quality for an X-ray Calcd for Ir2ClP4F402C52BH,: C, 46.84; H, 3.48. Found C, 46.76; study were obtained by the slow diffusion of diethyl ether into H, 3.54. a saturated acetone solution of the complex. The crystals proved Method B. T o a slurry of 3 (200 mg, 0.156 mmol) in 10 mL to be air stable so one was mounted on a glass fiber in the air and of THF under dinitrogen was added dropwise 1equiv of AgBF, no special precautions were taken. Unit cell parameters were (30.4 mg, 0.156 mmol) in 2 mL of THF. The color immediately obtained from a least-squares refinement of the setting angles changed to bright yellow, and upon continued stirring a yellow of 25 reflections, in the range 18.0' 5 28 5 24.0', which were precipitate appeared. The solution was taken to dryness under accurately centered on an Enraf-Nonius CAD4 diffractometer a stream of dinitrogen. The product was extracted from the using Mo Kcu radiation. The lack of systematic absences and the silver-containing products by adding 10 mL of CH2C12,filtering I diffraction symmetry were consistent with the space groups P1 under dinitrogen to give a clear bright yellow solution. Product and Pi. The centrosymmetric space group was chosen and later precipitation was induced by the addition of 30 mL of diethyl verified by the successful refinement of the structure with acether. The resulting bright yellow solid, obtained in 85% yield, ceptable positional parameters, thermal parameters, and agreewas in all spectroscopic properties identical with the product ment indices. A cell reduction failed to show the presence of a obtained from method A. higher symmetry cell." (d) [Ir,(H)Cl,(CH30,CC=CHCOzCH3)(CO)2(DPM)2]~ CH,C12 (6). T o a solution of 3 (200 mg, 0.156 mmol) in 10 mL of CH2Clzunder dinitrogen was added 1 equivalent to dimethyl (11) The cell reduction was performed by using a modification of TRACER 11 by S. L. Lawson. See: Lawson, S. L.; Jacobsen, R. A. "The Reduced Cell and ILs Crystallographic Applications", Ames Laboratory (10)Typically a 1:l electrolyte such as [Rh,(CO),(e-Cl)(r-CO)Report IS-1141; USAEC: Iowa State University, Ames, IA, April 1965. (DPM)21[BF,] gives a value of ca. 45 V' cm2 mol-' in CH&

Organometallics, Vol. 4, No. 10, 1985 1803

Diphosphine-Bridged I r i d i u m Complexes Table 11. Summary of Crystal Data and Details of Intensity Collection compd fw formula cell parameters 15.978 (2) 20.460 (5) 21.494 (2) C, A . 107.86 (2) a,deg 90.46 (2) 8, deg 106.17 (2) 7,deg 6389.8 v, A3 1.628 d(calcd), g/cm3 pi (z = 4) space group 22 temp, "C graphite-monchromated Mo K a radiatn (A, A) (0.710 69) 2.00 + 1.00 tan 8 wide X 4.0 receiving aperture, mm high, 173 from crystal 3.0 takeoff angle, deg variable between 6.705 and 1.059 scan speed, deg/min 0.75 + 0.347 tan 6 in w scan width 0.6 5 26 5 46.0 26 limits, deg 17756 (+h,i k , 3d) no. of unique data collected 11275 no. of unique data used 0.32914.4477 range of transmissn factors final no. of Darameters refined 545 error in observn of unit weight 2.960 R 0.061 RW 0.090 a, A

b, 8,

Intensity data were collected on a CAD4 diffractometer in the bisecting mode employing the w-28 scan technique up t o 28 = 46.0" with graphite-monochromated Mo K a radiation. Backgrounds were scanned for 25% of the peak width on either end of the peak scan. T h e intensities of three standard reflections were measured every 1h of exposure t o assess possible crystal decomposition or movement. No significant variation in these standards were observed so no correction was applied to the data. A total of 17 756 unique reflections were measured and processed in the usual way by using a value of 0.04 for p;12of these 11275 were considered t o be observed and were used in subsequent calculations. Absorption corrections were applied to the data by using Gaussian i n t e g r a t i ~ n . ' ~See Table I1 for pertinent crystal data and details of data collection. S t r u c t u r e Solution and Refinement. The structure was solved in the space group PI with two individual dimers per asymmetric unit. T h e positions of the four syntheses Ir atoms were obtained by using a iombination of direct methods and Patterson techniques. Subsequent refinements and difference Fourier calculations led to the location of the other atoms. Atomic scattering factors were taken from Cromer and Waber's tabulation14 for all atoms except hydrogen, for which the values of Stewart et al.lSwere used. Anomalous dispersion termsI6 for Ir, C1, and P were included in F,. T h e carbon atoms of all phenyl rings were refined as rigid groups having D 6 h symmetry, C-C distances of 1.392 A, and independent isotropic thermal parameters. All hydrogen atoms of the D P M ligands were located and included as fixed contributions in the least-squares refinements but were not themselves refined. Their idealized positions were calculated from the geometries about their attached carbon atoms using C-H distances of 0.95 A. Hydrogen atoms were assigned isotropic thermal parameters of 1A2 greater than the isotropic thermal parameter of their attached carbons. The olefinic hydrogens attached to carbons C(5A), C(5B), C(6A), and C(6B) were located and were included as fixed contributions as described above. No attempt was made to locate the methyl hydrogens of (12) Doedens, R. I.; Ibers, J. A. Znorg. Chem. 1967,6, 204. (13) For the programs used in the solution and refinement see ref 7. (14) Cromer, D. T.; Waber, J. T. 'International Tables for X-ray Crystallography";Kynock Press: Birmingham, England, 1974; Vol. IV, Table 2.2 A. (15) Stewart, R.F.; Davidson, E. R.; Simpson, W. T. J. Chem. Phys. 1965,42, 3175.

(16) Cromer, D. T.; Liberman, D. J. Chem. Phys. 1970,53, 1891.

8

C(161

F i g u r e 1. Perspective view of one of the two independent molecules (dimer A) of [IrzC1z(CH30zCC=CHC02CH,),(C0)2(DPM),] showing the numbering scheme. The numbering on the phenyl carbon atoms starts a t the ones bonded to phosphorus and increases sequentially around the ring. The 20% thermal ellipsoids are shown for all atoms except hydrogen which are shown artifically small. the methoxycarbonyl substituents. In the final refinements only the Ir, C1, and P atoms were refined anisotropically owing to the large number of variables and the resulting high cost of the least-squares calculations. The final model with 545 parameters varied refined to R = 0.061 and Rw = 0.090.'' On the final difference Fourier map, the 20 highest peaks (1.01-0.34 e A-3) were in the vicinities of the iridium and chlorine atoms. A typical carbon on earlier syntheses had a peak intensity of about 4.0 e A-3. The final positional parameters of the individual non-hydrogen atoms and the phenyl groups are given in Tables I11 and IV, respectively. The derived hydrogen positions, their thermal parameters, and a listing of observed and calculated structure amplitudes used in the refinements are available.l8

Description of Structure The title complex 7 crystallizes in the space group Pi with two independent dimers per asymmetric unit. Although the dimers differ in their relative orientations, all the analogous bond lengths and angles (see Tables V and VI) associated with each are very similar confirming that there is no major difference between them. A perspective view of molecule A, including the numbering scheme, is shown in Figure 1. A view of the approximate equatorial plane of the metals is shown in Figure 2 along with some relevent average bond lengths and angles. The overall geometry of the complex is essentially as expected for a binuclear species bridged by two mutually trans DPM ligands. Within the DPM framework, the bond lengths and angles are all normal (Tables V and VI) and similar to those found in other DPM-bridged complexes of i r i d i ~ m . ' - ~ , 'Each ~ ~ ~ ~metal has a slightly distorted octahedrd geometry in which the coordination sites are occupied by the two trans phosphorus atoms, a carbonyl group, a chloride ligand, a metalated olefin, and the Ir-Ir bond. The major distortion from octahedral geometry about each metal occurs in the P-Ir-P angles which are ca. 165.1O rather than 180° with all of the phosphorus atoms bent slightly toward the C1 ligands. T h i s bending seems to arise in order to relieve some of the severe steric crowding in the complex. Each molecule possesses approximate Czvgeometry with a pseudomirror plane running

(19) K&iak, C. P.;Woodcock, C.; Eisenberg, R. Inorg. Chem. 1980, 19,2733. (20) Cowie, M.;Sutherland, B. R., unpublished results.

1804 Organometallics, Vol. 4 , No. 10, 1985

atom

XU

0.42371 (5) -0.24685 (5) 0.25200 (4) -0.07859 (5) 0.3756 (4) -0.2940 (4) 0.2060 (4) -0.1243 (5) 0.4776 (3) -0.3161 (3) 0.3049 (3) -0.1487 (3) 0.3587 (3) -0.1894 (3) 0.1841 (3) -0.0182 (3) 0.4829 (9) -0.1806 (9) 0.3072 (9) -0.0274 (9) 0.6620 (12) -0.3622 (10) 0.1647 (10) 0.1525 (10) 0.6936 (12) -0.5425 (11) -0.0308 (10) 0.2090 (11) 0.5783 (11) -0.3970 (10) 0.0908 (10) 0.1091 (9) 0.6487 (10) -0.5572 (10) -0.0674 (9) 0.1398 (9)

Sutherland a n d Cowie

Table 111. Positional and Isotropic Parameters for the Non-Group Atoms y z B , A2 atom X Y 0.24036 (4) -0.15032 (3) 2.75' C(1A) 0.4577 (12) 0.3378 (10) 0.24364 (4) 0.35311 (3) 2.73' -0.2060 (12) 0.3403 iioj 0.24104 (4) -0.20866 (3) 2.82' 0.2867 (12) 0.3375 (11) 0.24376 (4) 0.28990 (3) 2.70b -0.0478 (12) 0.3414 (10) 7.1b 0.1129 (4) -0.1863 (3) 0.3869 (11) 0.1783 (9) 0.1163 (4) 0.3123 (3) 7.1b -0.2664 (11) 0.1848 (9) 0.1141 (4) -0.2462 (3) 7.6b 0.2406 (11) 0.1791 (9) 0.2554 (3) 0.1168 (4) 7.8b -0.1035 (11) 0.1842 (9) 0.2210 (3) -0.2533 (2) 3.3' 0.5384 (13) 0.2380 (10) 0.2535 (2) 0.2327 (2) 2.4b -0.3651 (11) 0.2410 (9) 0.2242 (2) -0.3126 (2) 3.2b 0.1339 (12) 0.2383 (10) 0.1871 (2) 0.2255 (2) 3.0b 0.0406 (11) 0.2410 (9) -0.0558 (2) 3.0b 0.5591 (12) 0.1765 (10) 0.2256 (2) 0.2265 (2) 3.0b 0.4462 (2) -0.4252 (12) 0.1822 (19) 3.2b 0.2241 (3) -0.1161 (2) 0.0670 (13) 0.1798 (10) 2.7b 0.2297 (2) 0.3825 (2) 0.0573 (13) 0.1824 (10) 4.7 (3) 0.3987 (7) -0.1133 (6) 0.6040 (15) 0.3089 (12) 5.0 (3) -0.3769 (13) 0.3129 (11) 0.4013 (7) 0.4037 (7) -0.1577 (7) 5.5 (3) 0.3977 (8) 0.1252 (14) 0.3081 (11) 4.9 (3) 0.4038 (7) 0.1059 (13) 0.3121 (10) 0.3325 (6) 0.3383 (10) -0.0951 (9) 8.0 (5) 0.6378 (15) 0.1764 (12) 6.1 (4) 0.4830 (8) 0.3470 ( 8 ) -0.5099 (13) 0.1848 (11) 0.3377 (8) -0.2919 (8) -0.0116 (13) 0.1775 (11) 6.2 (4) 0.3379 (8) 0.3184 (7) 0.1409 (13) 0.1816 (11) 5.7 (3) 0.2289 (10) -0.0395 (9) 0.6294 (21) 0.4156 (17) 8.2 (5) 0.2338 (9) -0.3929 (24) 0.4213 (20) 0.4368 (8) 7.1 (4) -0.3220 (8) 0.0960 (20) 0.4155 (17) 0.2311 (8) 6.2 (4) 0.1944 (8) 7.2 (4) 0.1718 (17) 0.4191 (14) 0.2309 (9) 0.7244 (17) 0.1049 (14) 0.3383 (9) -0.0128 (8) 6.8 (4) -0.6477 (17) 0.1103 (13) 6.0 (4) 0.3807 (7) 0.3391 (8) -0.1479 (16) 0.1093 (13) 6.1 (4) 0.3392 (8) -0.2037 (8) 0.2223 (7) 0.2198 (16) 0.1089 (13) 4.9 (3) 0.3460 (7) 0.5118 0.1329 5.9 (4) -0.0863 (7) 0.1113 (8) -0.4111 0.1373 0.4224 (7) 0.1177 (8) 6.1 (4) 0.0700 5.6 (3) 0.1356 -0.3459 (7) 0.1137 (8) 0.0123 0.1373 0.1153 ( 7 ) 0.1443 (7) 5.3 (3)

z

-0.1273 (9) 0.3818 isj -0.1787 (9) 0.3169 (9) -0.3169 (8) 0.1865 (8) -0.0781 (8) 0.4225 (9) -0.1041 (9) 0.3930 (8) -0.2533 (9) 0.2492 (8) -0.1097 (9) 0.3938 (9) -0.2816 (9) 0.2104 (9) -0.0683 (12) 0.4250 (10) -0.2546 (10) 0.2659 (10) -0.0752 (11) 0.4212 (IO) -0.3193 (10) 0.1831 (10) 0.0243 (16) 0.4124 (18) -0.1968 (15) 0.2445 (13) -0.0541 (13) 0.4487 (12) -0.3836 (12) 0.1149 (12) -0.1356 0.3801 -0.2764 0.1992

B , A2 3.4 (4) 3.5 iij 4.0 (4) 3.6 (4) 3.0 (3) 3.2 (4) 3.1 (3) 3.5 (4) 4.0 (4) 3.1 (4) 3.5 (4) 2.8 (3) 3.7 (4) 3.8 (4) 3.9 (4) 4.0 (4) 5.6 (5) 4.2 (4) 4.7 (5) 4.0 (4) 5.3 (5) 4.3 (4) 4.1 (4) 4.3 (4) 10.1 (9) 12.5 (11) 9.7 (9) 7.3 (7) 7.3 (6) 6.9 (6) 6.3 (6) 6.5 (6) 4.6 4.8 4.5 5.0

Estimated standard deviations in the last significant figures are given in parentheses in this and all subsequent tables. bEquivalent isotropic B's for anisotropic atoms

Figure 2. Representation of the complex in the approximate plane of the metals and the metrAed olefin groups. Some r t s a n t parameters, averaged over the two independent dimers, are shown. perpendicular to the Ir-Ir bond (see Figure 2). The iridium-iridium distances of 3.0128 (10) and 3.0216 (10) A are extremely long and fall outside the range normally associated with Ir-Ir single bonds in analogous IrDPM systems (range 2.779 (1)-2.893 (2) A).7v9,19*20 However, electron-counting rules require a formal metal-metal bond, otherwise each metal would have a 17-electron configuration and consequently be paramagnetic, for which there is no evidence. The long metal-metal separation is possibly a result of the steric crowding about the Ir atoms. Bringing the metals closer together would result in highly unfavorable interactions between the two chlorine atoms and the two carbonyl groups. These distances are already rather short, at ca. 2.99 and 2.92 A, respectively. In a somewhat analogous complex, [Ir2C14(C0)2(DPM)2], which also has pseudooctahedral Ir centers and cis C1 ligands, the

metal-metal distance has a more typical value of 2.786 (1)

A.20 However, in this case the molecule is twisted about

the Ir-Ir bond by ca. 27.7" such that the ligands on one metal are staggered with respect to those on the other metal, reducing the unfavorable contacts and allowing a normal metal-metal interaction. In the present complex both halves of the molecule are almost exactly eclipsed. It seems that staggering about the two metals is not possible owing to the unfavorable contacts that would result between the metalated olefins and the DPM phenyl groups. In another crowded binuclear complex containing pseudooctahedral metal centers, [Rh,(CN-t-Bu),(pCF3C2CF3)(DPM),][PF6]2,21the molecule was found to be ~

_ _ _ _ _ ~ ~ ~

~

(21) Mague, J. T. Inorg. Chem. 1983, 22, 1158.

Organometallics, Vol. 4, No. 10, 1985 1805

Diphosphine-Bridged Iridium Complexes

Table IV. Derived Parameters for the Rigid-Group Atoms of [Ir2C12(CH302CC=CHCO~CH3)2(CO)2(DPM)21 X Y z B , A2 atom X Y 2 B, A2 4.1 (4) C(G31A) 0.3566 (9) 0.3013 (7) -0.3426 (7) 4.2 (4) -0.2780 (8) 0.2948 (7) 0.5511 (9) C(GI1A) atom

C(G12A) C(G13A) C(G14A) C(G15A) C(G16A) C(G11B) C(G12B) C(G13B) C(G14B) C(G15B) C(G16B) C(G21A) C(G22A) C(G23A) C(G24A) C(G25A) C(G26A) C(G21B) C(G22B) C(G23B) C(G24B) C(G25B) C(G26B) C(G51A) C(G52A) C(G53A) C(G54A) C(G55A) C(G56A) C(G51B) C(G52B) C(G53B) C(G54B) C(G55B) C(G56B) C(G61A) C(G62A) C(G63A) C(G64A) C(G65A) C(G66A) C(G61B) C(G62B) C(G63B) C(G64B) C(G65B) C(G66B)

0.6037 (11) 0.3562 (9) 0.6605 (11) 0.4103 (8) 0.6647 (10) 0.4031 (8) 0.6121 (11) 0.3417 (10) 0.2876 (7) 0.553 (10) -0.3244 (10) 0.3100 (6) 0.3758 (8) -0.2607 (8) -0.2672 (10) 0.4360 (6) -0.3375 (13) 0.4304 (8) -0.4013 (10) 0.3646 (11) 0.3044 (8) -0.3947 (9) 0.1567 (7) 0.5416 (9) 0.0834 (7) 0.5029 (7) 0.5537 (10) 0.0364 (5) 0.0627 (8) 0.6433 (9) 0.1360 (8) 0.6820 (7) 0.1830 (6) 0.6312 (9) -0.4272 (7) 0.1714 (6) 0.0984 (7) -0.4448 (8) -0.5305 (10) 0.0534 (5) -0.5986 (7) 0.0814 (8) -0.5811 (8) 0.1544 (8) -0.4954 (10) 0.1994 (6) 0.2994 (7) 0.3621 (9) 0.3859 (10) 0.3699 (8) 0.3915 (11) 0.4262 (6) 0.3734 (11) 0.4121 (7) 0.3496 (10) 0.3416 (9) 0.3439 (9) 0.2853 (6) -0.1456 (8) 0.3015 (6) -0.1680 (8) 0.3650 (7) -0.1339 (10) 0.4218 (6) -0.0774 (10) 0.4151 (7) -0.0550 (9) 0.3516 (8) 0.2948 (6) -0.0891 (9) 0.1630 (6) 0.3929 (8) 0.3505 (7) 0.0895 (7) 0.3777 (9) 0.0430 (5) 0.4474 (10) 0.0699 (8) 0.1434 (8) 0.4899 (8) 0.4626 (8) 0.1900 (5) -0.2643 (8) 0.1630 (6) -0.2836 (9) 0.0893 (7) 0.0415 (5) -0.3427 (9) -0.3825 (9) 0.0673 (7) -0.3633 (10) 0.1410 (8) -0.3042 (9) 0.1888 (5)

-0.2306 -0.2495 (8) -0.3158 (10) -0.3632 (6) -0.3443 (7) 0.2343 (7) 0.2616 (7) 0.2469 (8) 0.2049 (1) 0.1777 (8) 0.1924 (8) -0.2698 (7) -0.3003 (7) -0.3113 (7) -0.2918 (8) -0.2613 (8) -0.2503 (7) 0.2360 (7) 0.2022 (7) 0.1910 (7) 0.2136 (8) 0.2475 (8) 0.2586 (7) 0.0194 (5) 0.0185 (6) 0.0762 (1) 0.1348 (7) 0.1357 (5) 0.0781 (7) 0.5213 (5) 0.5332 (6) 0.5909 (7) 0.6366 (6) 0.6247 (6) 0.5670 (7) -0.0246 (6) -0.0477 (6) -0.0224 (7) 0.0266 (7) 0.0502 (6) 0.0249 (7) 0.4778 (6) 0.4464 (5) 0.4709 (7) 0.5268 (7) 0.5581 (6) 0.5336 (6)

C(G32A) C(G33A) C(G34A) C(G35A) C(G36A) C(G31B) C(G32B) C(G33B) C(G34B) C(G35B) C(G36B) C(G41A) C(G42A) C(G43A) C(G44A) C(G45A) C(G46A) C(G41B) C(G42B) C(G43B) C(G44B) C(G45B) C(G46B) C(G71A) C(G72A) C(G73A) C(G14A) C(G75A) C(G76A) C(G71B) C(G72B) C(G73B) C(G74B) C(G75B) C(G76B) C(G81A) C(G82A) C(G83A) C(G84A) C(G85A) C(G86A) C(G81B) C(G82B) C(G83B) C(G84B) C(G85B) C(G86B)

7.4 (6) 10.5 (5) 7.7 (7) 6.5 (6) 6.9 (6) 3.2 (4) 5.5 (5) 6.9 (6) 7.4 (6) 11.6 (11) 8.6 (8) 4.3 (4) 5.0 (5) 6.4 (6) 6.4 (6) 6.2 (6) 5.6 (5) 3.9 (4) 4.4 (4) 6.5 (6) 6.8 (6) 6.9 (6) 5.2 (5) 3.8 (4) 6.9 (6) 8.5 (7) 6.9 (6) 5.7 (5) 5.6 (5) 3.5 (4) 4.4 (4) 5.9 (5) 6.4 (6) 7.0 (6) 5.4 (5) 3.2 (3) 5.4 (5) 5.5 (5) 6.0 (5) 8.0 (7) 5.3 (5) 3.4 (4) 4.4 (4) 5.7 (5) 6.3 (6) 6.5 (6) 5.1 (5)

0.3899 (11) 0.4327 (11) 0.4422 (10) 0.4090 (11) 0.3661 (10) -0.1366 (9) -0.0646 (8) -0.0536 (8) -0.1148 (11) -0.1868 (9) -0.1978 (7) 0.2232 (8) 0.2144 (9) 0.1534 (11) 0.1011 (9) 0.1099 (10) 0.1709 (10) -0.1197 (8) -0.1537 (8) -0.1287 (9) -0.0697 (10) -0.0357 (9) -0.0607 (8) 0.1691 (9) 0.1695 (10) 0.1526 (11) 0.1351 (10) 0.1347 (11) 0.1517 (10) 0.0484 (8) 0.0369 (9) 0.0851 (10) 0.1448 (10) 0.1563 (9) 0.1081 (10) 0.0767 (7) 0.0599 (8) -0.0259 (10) -0.0948 (7) -0.0780 (8) 0.0077 (10) 0.0491 (8) 0.0118 (7) 0.0632 (10) 0.1519 (9) 0.1891 (7) 0.1377 (9)

0.3703 (9) 0.4270 (6) 0.4145 (8) 0.3455 (9) 0.2889 (6) 0.3010 (6) 0.3620 (7) 0.4168 (6) 0.4106 (7) 0.3496 (9) 0.2948 (6) 0.1615 (7) 0.0882 (8) 0.0415 (6) 0.0680 (9) 0.1413 (9) 0.1880 (6) 0.1620 (6) 0.0886 (7) 0.0397 (5) 0.0641 (7) 0.1376 (8) 0.1865 (5) 0.2982 (7) 0.3626 (8) 0.4170 (6) 0.4070 (8) 0.3426 (9) 0.2881 (7) 0.3058 (6) 0.3732 (8) 0.4317 (6) 0.4228 (7) 0.3555 (9) 0.2969 (7) 0.1624 (7) 0.0886 (7) 0.0437 (5) 0.0725 (8) 0.1463 (9) 0.1912 (6) 0.1680 (6) 0.0953 (7) 0.0488 (5) 0.0749 (8) 0.1476 (8) 0.1942 (6)

-0.2981 (5) -0.3202 (8) -0.3868 (9) -0.4312 (6) -0.4091 (7) 0.1551 (6) 0.1772 (6) 0.1496 (7) 0.1001 (7) 0.0780 (6) 0.1056 (7) -0.3803 (6) -0.4008 (7) -0.4533 (8) -0.4852 (7) -0.4648 (8) -0.4123 (8) 0.1181 (5) 0.1076 (6) 0.0560 (7) 0.0150 (6) 0.0255 (6) 0.0771 (7) -0.0489 (6) -0.0583 (6) -0.0074 (9) 0.0529 (7) 0.0623 (6) 0.0114 (8) 0.4491 (6) 0.4595 (7) 0.5118 (8) 0.5537 (6) 0.5433 (7) 0.4910 (8) -0.1373 (7) -0.1512 (7) -0.1666 (7) -0.1681 (8) -0.1542 (8) -0.1388 (8) 0.3637 (7) 0.3550 (7) 0.3399 (7) 0.3335 (8) 0.3422 (8) 0.3573 (7)

6.5 (6) 9.1 (8) 7.1 (6) 6.3 (6) 6.7 (6) 3.2 (4) 5.5 (5) 5.7 (5) 6.1 (5) 7.3 (6) 5.6 (5) 3.8 (4) 5.6 (5) 6.9 (6) 7.1 (6) 8.3 (8) 6.2 (6) 3.4 (4) 4.4 (4) 5.7 (5) 5.8 (5) 6.0 (6) 4.4 (4) 3.4 (4) 6.7 (6) 8.1 (7) 6.6 (6) 7.8 (7) 6.6 (6) 3.6 (4) 5.5 (5) 6.3 (6) 6.3 (6) 9.0 ( 8 ) 5.9 (5) 3.7 (4) 4.8 (5) 6.0 (5) 6.7 (6) 7.2 (6) 6.3 (6) 3.6 (4) 4.5 (4) 6.0 (5) 7.0 (6) 6.3 (6) 6.1 (5)

Rigid-Group Parameters x,"

ring 1A ring 2A ring 3A ring 4A ring 5A ring 6A ring 7A ring SA ring 1B ring 2B ring 3B ring 4B ring 5B ring 6B ring 7B ring 8B

0.6079 (7) -0.3310 (7) 0.5924 (6) -0.5129 (6) 0.3994 (6) -0.1257 (6) 0.1622 (6) -0.0947 (6) 0.3677 (6) -0.1115 (6) 0.4202 (6) -0.3234 (6) 0.1521 (6) 0.0966 (6) -0.0091 (6) 0.1005 (6)

YC

2,

6

t

9

0.3490 (6) 0.3702 (6) 0.1097 (5) 0.1264 (5) 0.3579 (6) 0.3558 (5) 0.1148 (6) 0.1131 (5) 0.3558 (5) 0.3583 (5) 0.1165 (5) 0.1151 (5) 0.3526 (6) 0.3643 (5) 0.1175 (5) 0.1215 (5)

-0.2969 (6) 0.2196 (5) -0.2808 (4) 0.2248 (4) -0.3647 (5) 0.1276 (4) -0.4328 (5) 0.0665 (4) 0.0771 (5) 0.5790 (4) 0.0013 (4) 0.5023 (4) 0.0020 (5) 0.5014 (5) -0.1527 (4) 0.3486 (4)

2.11 (3) 1.768 (11) -1.044 (9) 0.382 (10) 2.73 (3) 1.722 (10) 0.280 (9) -0.671 (9) 2.822 (12) -2.602 (9) -1.010 (10) 0.200 (12) 3.000 (13) -2.661 (10) 0.340 (9) -0.925 (8)

1.94 (1) 2.618 (10) -2.794 (9) -2.604 (9) 1.956 (9) 2.593 (9) 3.072 (9) 2.817 (8) -2.580 (9) -2.904 (8) -2.567 (8) -2.288 (8) -2.494 (9) -2.919 (9) -3.001 (9) 3.079 (9)

-1.28 (3) -0.243 (11) -0.235 (9) -3.062 (10) -1.68 (3) -0.511 (10) -2.361 (9) -0.977 (9) 1.461 (11) 2.157 (9) 0.419 (10) 2.435 (13) 1.296 (12) 2.320 (9) -3.010 (9) -0.284 (9)

O x c , ye, and t, are the fractional coordinates of the centroid of the rigid group. bThe rigid group orientation angles 6, e, and 7 (radians) are the angles by which the rigid body is rotated with respect to a set of axes x , y , and z. See: La Placa, S. J.; Ibers, J. A. Acta Crystallogr. 1965, 18, 511.

twisted about the Rh-Rh axis by ca. 20.3' and the Rh-Rh distance is still very long (2.9653 (6) A) although the complex again has a metal-metal bond. It is also possible that the long Ir-Ir bond in 7 is a result of the high trans

influence of the two metalloolefin groups which lie opposite the Ir-Ir bond. The Ir-C1 distances and the parameters involving the carbonyl ligands are all normal and compare well with

1806 Organometallics, Vol. 4, No. 10, 1985

Sutherland and Cowie

Table V. Selected Distances (A) in [Ir2C12(CH302CC=CHC02CH,)2(C0)2(DPM)2] Bonding Distances dimer A dimer B dimer A dimer B 3.0128 (10) 3.0216 (10) 1.24 (2) 1.22 (2) 2.372 (8) 2.371 ( 7 ) 1.29 (2) 1.30 ( 2 ) 2.362 (8) 2.364 (8) 1.30 (2) 1.32 (2) 2.342 (5) 2.320 (5) 1.34 (2) 1.38 (2) 2.353 (5) 2.355 (5) 1.31 (2) 1.35 (2) 2.354 ( 5 ) 2.346 (5) 1.52 (3) 1.59 (4) 2.345 (5) 2.335 (5) 1.50 (3) 1.48 ( 3 ) 1.82(2) 1.80 (2) 1.45 (3) 1.54 ( 3 ) 1.80 (2) 1.82 (2) 1.48 (3) 1.45 ( 3 ) 2.10 (2) 2.08 (2) 1.81 (2) 1.80 ( 2 ) 2.09 (2) 2.11 ( 2 ) 1.80 (2) 1.83 (2) 1.14 (2) 1.14 (2) 1.84 (2) 1.81 (2) 1.12 (2) 1.16 (2) 1.80 (2) 1.81 (2) 1.36 (2) 1.32 (2) 1.79 (2) 1.86 (2) 1.33 (2) 1.33 (2) 1.84 (2) 1.82 (1) 1.50 (3) 1.48 (2) 1.87 (2) 1.84 ( 2 ) 1.48 (3) 1.47 (2) 1.83 (1) 1.81 (1) 1.45 ( 3 ) 1.49 (3) 1.83 (1) 1.82 (1) 1.47 (3) 1.46 ( 3 ) 1.82 (2) 1.81 (1) 1.21 ( 2 ) 1.21 (2) 1.82 (1) 1.81 (1) 1.22 ( 2 ) 1.23 (2) 1.78 (1) 1.83 ( 2 ) 1.22 (2) 1.21 (2) dimer A P(1)-P(2) P(3)-P(4) H(l)-Cl( 1) H(2)-C1(2)

3.057 ( 7 ) 3.056 (7) 2.30 2.45

Nonbonding- Distances dimer B Cl(l)-C1(2) 3.061 (6) 3.061 (7) c (11-c(2) 2.43 O( 1)-0(2) 2.50

values previously r e p ~ r t e d . ~ - ~ J ~ ~ ~ ~ As can be seen in Figures 1 and 2, the alkyne molecules have inserted into the two original 1H bonds forming two metalloolefin linkages, in which the C02CH3groups are mutually cis about the C=C bonds. The C=C distances (average 1.34 A) are typical of carbon-carbon double bonds and the angles about these carbon atoms are all close to 120° (see Table VI), consistent with sp2hybridization. The Ir-C(o1efin) distances (average 2.10 A) are normal and compare well with similar values involving a-bonded carbon atoms.22,23Within each of the metalated olefin groups, one C02CH3group lies in the metal-olefin plane while the other is essentially perpendicular to it, again likely a result of intramolecular nonbonded contacts. As a result, the C=O fragment of one of the COzCH3groups is coplanar with the olefin linkage and could in principle be conjugated with it. However, as the bond lengths indicate, there is no significant difference between the two COzCHBgroups of each metalated olefin. All of the bond lengths and angles associated with the olefin atoms are unexceptional and similar to those observed in other structure^.^^^ One feature of note concerning the metalloolefin groups is that the severe crowding around the metals leads to rather short olefinic hydrogen-chlorine contacts of ca. 2.42 A. Discussion and Results Placing an atmosphere of H2 over a solution of trans[IrCl(CO)(DPM)]z,1, produces an immediate reaction as evidenced by a rapid color change from purple to yellow. The new compound 3 which is isolated from this solution displays two distinct terminal carbonyl bands (2012,1972 cm-l) and two terminal hydride bands (2222,2091 cm-') in the infrared spectrum while analyses indicate the presence of two chlorines per dimer. On the basis of this (22) Diversi, P.; Ingrosso, G.; Lucherini, A,; Porzio, W.; Zocchi, M. Inorg. Chem. 1980, 19; 3590. (23) Crabtree, R. H.; Quirk, J. M.; Felkin, H.; Fillebeen-Khan, T.; Pascard, C. J . Organomet. Chem. 1980, 187, C32.

dimer B 2.982 (9) 2.89 (2) 2.89 (2)

dimer A 3.000 (9) 2.94 (3) 2.95 (2)

information, 3 is formulated to have the structure shown below in the solid state. This geometry is analogous to PP -

1

,LO

C I-I-'r

j

,xi Ir'-CO

H/'

H 1'

P

vp 3

that postulated for the products of the reaction of 1 with alkynes, and confirmed by an X-ray structure of the DMA adducte8 The spectroscopic parameters for 3 and these alkyne adducts are very similar. Evidence that the two hydride ligands are not on the same metal comes from selective phosphorus decoupled 'H NMR experiments (vide infra). The conversion of 1 to 3 can readily be reversed by gently warming the solution under Nzfor several minutes, suggesting that the two hydride ligands are mutually cis. With mononuclear octahedral bis(ph0sphine)iridium hydrides as a basis for comparison, the carbonyl and iridium-hydride stretches of 3 can be assigned. In mononuclear systems, Ir-H stretches, when H is trans to CO, are generally observed in the range 2100-2000 cm-', while those when the hydride ligand is trans to ligands such as halides occur around 2240-2180 ~ m - ' . A ~ similar ~ trend is observed for the carbonyl bands; where CO is trans to a hydride ligand, v(C0) occurs a t ca. 1980 cm-', while the carbonyl stretch when CO is trans to a chloride ligand is observed at ca. 2025 With this information, we assign the carbonyl stretch at 1972 cm-' as due to the group opposite the hydride ligand and that at 2012 cm-' as the CO opposite the Ir-Ir bond. Similarly, the Ir-H stretch at 2222 cm-' would appear to arise from the hydride ligand opposite the chloro ligand and that a t 2091 cm-' due to the hydride opposite the carbonyl group. The observed (24)

Kaesz, H. D.; Saillant, R. B. Chem. Reu. 1972, 72, 231

Diphosphine-Bridged Iridium Complexes

Organometallics, Vol. 4, No. 10, 1985 1807

Table VI. Selected Angles (des) in [Ir2C12(CH302CC=CHCOzCH3)2(C0)2(DPM)2] dimer A dimer B dimer A dimer B 123 (2) 126 (2) 0(3)-C(9)-0(7) 89.7 (1) P(lkIr(l)-Ir(2) 90.7 (1) 123 i2j 125 (2) 0(4)-C( l0)-0(8) 91.4 (1) 90.2 (1) ~(3)-1r(1)-1r(2) 120 (2) 119 (2) 0(5)-C( 11)-0(9) 91.2 (1) 90.4 (1) P(2)-Ir(2)-Ir(l) 119 (2) 119 (2) 0(6)-C(12)-0(10) 89.6 (1) 90.9 (1) P(4)-Ir(2)-Ir(l) 111 (2) 117 (2) C (9)-0 (7)-C (13) 167.1 (1) 163.4 (2) P(1)-Ir( 1)-P(3) 113 (2) 114 (2) C(10)-0(8)-C(14) 165.2 (2) 164.5 (2) P (2)-Ir (2)-P (4) 117 (2) 119 (2) C(11)-0(9)-C(15) 89.8 (2) 89.7 (2) Cl(l)-Ir(l)-Ir(2) 117 (2) 117 (2) C(12)-0(10)-C(16) 89.3 (2) 89.9 (2) C1(2)-Ir (2)-Ir (1) 114.7 (9) 115.9 (9) P(l)-C(3)-P(2) 82.2 (2) 83.2 (2) P(1)-Ir( l)-Cl( 1) 115 (1) 113.9 (9) P(3)-C(4)-P(4) 84.0 (2) 82.2 (2) P(3)-Ir(l)-Cl(l) 110.0 (6) 109.3 (6) Ir(l)-P(l)-C(3) 83.0 (2) 82.3 (2) P(2)-Ir(2)-Cl(2) 121.3 (4) 122.5 (4) Ir(l)-P(l)-C(Gll) 82.2 (2) 82.3 (2) P(4)-Ir(2)-Cl(2) 113.3 (5) 113.3 (5) Ir(l)-P(l)-C(G21) 96.6 (6) 95.6 (6) P(1)-Ir(l)-C(l) 108.9 (6) 108.7 (6) Ir(2)-P(2)-C(3) 96.3 (6) 99.9 (6) P(3)-Ir( 1)-C( 1) 120.6 (3) 122.0 (4) Ir(2)-P(2)-C(G31) 96.3 (6) 98.7 (6) P (2)-Ir (2)-C (2) 115.6 (4) 113.5 (4) Ir(2)-P(2)-C(G41) 98.5 (6) 96.7 (6) P(4)-Ir(2)-C(2) 108.6 (6) 109.0 (6) Ir (1)-P(3)-C (4) 88.4 (5) 93.2 (5) P(l)-Ir( 1)-C(5) 121.2 (4) 124.5 (4) Ir(l)-P(3)-C(G51) 90.3 (5) 85.7 (5) P (3)-Ir (1)-C (5) 115.2 (4) 113.9 (4) Ir(l)-P(3)-C(G61) 91.3 (5) 87.3 (5) P(2)-Ir(2)-C(6) 110.3 (6) 109.6 (6) Ir(2)-P(4)-C(4) 87.5 (5) 91.0 (5) P (4)-Ir (2)-C (6) 121.9 (5) 122.5 (5) Ir(2)-P(4)-C(G71) 177.0 (6) 176.7 (6) C1(1)-Ir (1)-C(l) 114.0 (4) 112.4 (5) Ir(2)-P(4)-C(G81) 177.8 (6) 179.0 (6) Cl(2)-Ir(2)-C(2) 104.9 (6) 100.9 (7) C(Gll)-P(l)-C(GBl) 89.0 (5) 89.2 (5) Cl(l)-Ir(l)-C(5) 105.6 ( 8 ) 105.6 (8) C(Gll)-P(l)-C(3) 89.2 (5) 85.5 (5) Cl(2)-Ir(2)-C(6) 103.5 (7) 95.3 (6) C(G21)-P(l)-C(3) 94.1 (7) 93.5 (8) C(l)-Ir(l)-C(5) 104.2 (6) 100.3 (6) C (G31)-P (2)-C (G41) 91.9 (8) 92.9 (7) C(2)-Ir(2)-C(6) 104.3 (2) 106.7 (8) C(G31)-P (2)-C (3) 87.3 (6) 87.7 (6) C(1)-Ir( 1)-Ir( 2) 103.1 (6) 102.0 (6) C(G41)-P (2)-C (3) 88.6 (6) 89.8 (7) C(2)-Ir (2)-Ir( 1) 101.1 (5) 102.1 (6) C(G51)-P(3)-C(G61) 177.8 (5) 175.8 (5) C(5)-1r(l)-Ir(2) 106.8 (6) 103.5 (7) C(G51)-P(3)-C(4) 176.9 (5) 177.3 (5) C(6)-Ir( 2)-Ir (1) 102.1 (7) 101.0 (7) C(G61)-P(3)-C(4) 176 (2) 177 (2) Ir (1)-C( 1)-0(1) 103.1 (6) 103.0 (6) 178 (2) C(G71)-P(4)-C(G81) 177 (2) Ir (2)-C (2)-0 (2) 104.0 (6) 105.1 (7) C (G71)-P (4)-C (4) 125 (1) 124 (1) Ir(l)-C(5)-C(7) 101.1 (8) 102.2 (7) 125 (1) C(G81)-P(4)-C(4) 126 (1) Ir(2)-C (6)-C(8) 120.0 (7) 114 (1) P(l)-C(Gll)-C(GlB) 120.3 (6) 117 (1) Ir (1)-C (5)-C (9) 120.1 (6) 119.7 (5) 113 (1) P(l)-C(Gll)-C(Gl6) 116 (1) Ir (2)-C(6)-C (10) 121.9 (5) 122.0 (5) 1 2 1 (2) P(l)-C(G21)-C(G22) 119 (2) C(7)-C(5)-C(9) 118.2 (5) 118.0 (4) 121 (2) P(l)-C(G21)-C(G26) 117 (2) C(S)-C(S)-C(lO) 120.2 (6) 120.7 (7) 122 (2) P(2)-C(G31)-C(G32) 122 (2) C(5)-C(7)-C(ll) 119.2 (5) P (2)-C (G31)-C (G36) 124 (2) 119.7 (5) 125 (2) C(S)-C(S)-C( 12) 119.9 (5) 112 P(2)-C(G41)-C(G42) 119 120.7 (6) C(5)-C(7)-H(1) 120.1 (4) 117 P(2)-C(G41)-C(G46) 119 119.3 (5) C(6)-C(8)-H(2) 120.8 (5) P(3)-C(G51)-C(G52) 120 120.0 (6) 125 C(ll)-C(7)-H(l) 119.2 (5) 117 P(3)-C(G51)-C(G56) 117 120.0 (5) C (12)-C (8)-H (2) 121.0 (5) 121.2 (6) P (3)-C (G61)-C (G62) 122 (2) 127 (2) C (5)-C (9)-0(3) 119.0 (5) 1 2 1 (2) P(3)-C(G2)-C(G66) 121 (2) 119.8 (5) C(6)-C(10)-0(4) 119.2 (6) 110 (2) 110 (2) P(4)-C(G71)-C(G72) 120.9 (6) C(5)-C(9)-0(7) 119.0 (6) 120.8 (5) 116 (2) 112 (2) P(4)-C(G71)-C(G76) C (6)-C (10)-0( 8) 120.4 (5) 123.2 (6) 130 (2) 126 (2) P(4)-C(G81)-C(G82) C(7)-C(ll)-O(5) 116.9 (5) 119.6 (5) 128 (2) 125 (2) P(4)-C(G81)-C(G86) C(8)-C (12)-0 (6) C(7)-C(ll)-0(9) 110 (2) 115 (2) 112 (2) 116 (2) C (8)-C (12)-0 (10)

intensities of these bands are also consistent with this argument (see Table I); in particular, the occurrence of vibrational coupling between the mutually trans H and CO ligands results in lowering of the v ( C 0 ) band intensity and an increase in the v(1r-H) i n t e n ~ i t y .Attempts ~~ to confirm these assignments by preparing the deuterated analogue of 3 were unsuccessful due to our reluctance to use the large amounts of Dz required to isolate this species as a solid. Examination of the solution IR spectra in both CH2C12and T H F also proved inconclusive due to the breadth of the bands and the appearance of additional ones arising from the complex nature of 3 in solution (vide infra). The assignment of the carbonyl bands is also consistent with those of the aforementioned alkyne adduct [Ir2Clz(CO)2(p-DMA)(DPM)z] where v(C0) trans to the metal-metal bond occurred at 2023 cm-l while that trans to the coordinated alkyne moiety appeared a t 1999 cm-'. In solution 3 displays complex behavior. At room temperature, the 31P(1HJNMR spectra show only two broad featureless peaks at ca. 6 -1 and -8. When the temperature is lowered to -40 " C , the pattern sharpens into a pair of

pseudotriplets at 6 -1.4 and -8.6 and a small singlet a t 6 -5.20. Further lowering of the temperature to about -60 "C causes the downfield pseudotriplet and the singlet to collapse into the base line while the upfield pseudotriplet remains unchanged. By -100 "C a new signal has reemerged underneath the upfield signal and results in the formation of an AA'BB' pattern centered at b -7.6. This last pattern is very analogous to that observed for [IrzC12(CO)2(p-DMA)(DPM),] at all temperatures*. These observations can be explained in terms of the set of equilibria shown in Scheme I. The low-temperature limiting spectrum (-100 " C ) arises from structures I and V which are identical and represent 3 as it occurs in the solid state. As the temperature is raised, chloride dissociation becomes significant allowing the equilibrium between 11, 111, and IV to occur. The low-temperature limiting spectrum for this equilibrium occurs at -40 "C where the equivalent structures I1 and IV give rise to the pair of pseudotriplets and I11 gives rise to the singlet. A similar equilibrium has previously been observed for [Ir,Cl(CO),(pDMA)(DPM),] [BF,] which was prepared by the

1808 Organometallics, Vol. 4, No. 10, 1985

Sutherland and Cowie Scheme I

P- P

P-P

abstraction of chloride ion from [IrzC1z(CO)z(~-DMA)(DPM)z].s The IH NMR data also support this scheme. At room temperature only two broad peaks are observed in the hydride region. Lowering the temperature to -80 "C produces two large triplets at -5.76 and -15.10 ppm, arising from the two inequivalent hydrides in I1 and IV, and one small triplet a t -14.86 ppm, arising from the symmetrical chloro-bridged intermediate I11 (see Table I). Unfortunately, the low-temperature limiting spectrum could not be obtained. Proton NMR experiments with selective 31Pdecoupling show that the 'H triplet at -5.76 ppm is coupled to the 31Presonance at -8.6 ppm while the triplet a t -15.10 ppm is coupled to the 31Presonance at -1.4 ppm. Therefore, irradiating each of the two phosphorus resonances in turn causes the respective hydride resonances to collapse into a broad singlet. Although CHZCl2solutions of 3 are nonconducting, the molar conductivity in nitromethane is only slightly less than a nomal 1:l electrolyte, supporting the suggestion of chloride dissociation from 3. Involvement of Hz loss in the above fluxional process is ruled out by placing a D2 atmosphere above solutions of 3; no deuterium incorporation is observed over the time required to record the above spectra. The cationic A-frame complex [Irz(CO)z(p-Cl)(DPM),][BF,], 2, also reacts rapidly with hydrogen to give a very pale yellow solution containing a single species 4. The 'H NMR spectrum indicates that 4 is a tetrahydride species resulting from the coordination of two molecules of hydrogen to 2 (see Table I). The 'H and 31PNMR spectra also indicate that 4 is fluxional in solution. The low-temperature limiting 'H spectrum shows four distinct terminal hydride resonances, three of which broaden and collapse into the base line as the temperature is raised while the fourth resonance, that which is most upfield, remains sharp. No limiting spectrum could be obtained in the 31P(1H}NMR spectra, but the room-temperature spectrum displays an AA'BB' pattern, suggesting that the time-averaged geometry of 4 is unsymmetrical. Placing D, above solutions of 4 has no affect on the 'H NMR spectrum after 15 min ruling out Hz loss as a step in the fluxional process. It is not clear from this information what the structure of 4 is or what processes are involved in the fluxional behavior. When a solution of 4 is refluxed in T H F for 20 min, a new species, 5 , is formed in quantitative yield. The 'H

NMR and IR spectra indicate that this species is a dicarbonyl dihydride species formed by the loss of one molecule of Hz from 4, and adding H2 to a solution of 5 readily regenerates 4. On the basis of the above data and the 31P{1HJ spectra which show a symmetrical species over all temperatures, there are two possible structures for 5 which are difficult to distinguish by spectroscopy alone. These structures are shown as VI and VII. Structure VI

+

PP -

+ PP-

p \ I p p l /

V I

VI1

appears to be correct based on the observation that prolonged refluxing of solutions of 5 fails to result in any H, loss, suggesting that the hydrides are not mutually cis. Structure VI is also consistent with the X-ray structure of the alkyne-inserted product 7 (vide infra). It is significant that the symmetrical species observed in CHZCl2 solutions of 3, and proposed to have a structure related to VII, has rather different spectral parameters from those of 5; this again suggests that 5 has structure VI. That species having structures VI and VI1 should have different spectral parameters is totally expected since for the former the carbonyl groups are pseudo-trans to the bridging chloro group, whereas for the latter it is the hydrides which are opposite the C1 ligand. Compound 5 can also be prepared by the reaction of 3 with AgBF,, suggesting that chloride abstraction is accompanied by a rearrangement. Since complexes 5 and 4 are related by the respective gain and loss of Hz, some ligand rearrangement must have occurred in the initial formation of 4 from the reaction of 2 with H2 if VI is the correct structure for 5 . Simple addition of 2 equiv of H2 to 2 without some rearrangement cannot produce a species which would generate 5 (having structure VI) upon Hz loss. Compound 3 reacts quantitatively with 1equiv of DMA to give rise to a new product, [Ir2HClZ(CH3O2CC= CHC02CH,)(CO),(DPM)2](6). The 'H NMR spectrum of 6 shows one hydride resonance at 6 -8.89 and a singlet at 6 3.85, each integrating as one hydrogen (see Table I). Similarly, the IR spectrum shows only one v(1r-H) band in addition to new v(C=O) and v(C=C) bands of the DMA

Organometallics, Vol. 4, No. 10, 1985 1809

Diphosphine-Bridged Iridium Complexes Scheme I1

It

P-P

R/c\H

6

ligand. This spectroscopic information, coupled with the observation of a 31P(1HJpattern typical of an unsymmetrical species, suggests the structure shown below for 6 in which the alkyne has inserted into one of the Ir-H bonds of 3. Although compound 3 is coordinatively saturated in the solid state and so would not be expected to react further, C1- dissociation from one iridium center occurs in solution yielding the unsaturated cationic intermediate 11, as pointed out earlier in Scheme I. Coordination of the alkyne at this metal, followed by insertion into the Ir-H bond and C1- recoordination, would yield 6 as shown in Scheme 11. Attempts to induce further reaction between the metalated olefin and the remaining hydride ligand have been unsuccessful. In order for further reaction to occur, it is apparent that an open coordination site and the concomitant coordinative unsaturation must be generated at the metal having the hydride ligand, either by loss of chloride ion or carbon monoxide. However, the removal of chloride ion by the reaction of 6 with AgBF4 does not proceed as suggested but leads only to the isolation of 7 (vide infra) in low yield (